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ToolsBull, James N., Stockett, Mark H., Chakraborty, Pratip, Ashworth, Eleanor K., Fatima, Anam, Esposito, Vincent J., Greetham, Gregory M., Malakar, Partha and Meech, Stephen R. (2025) Hot ground state cooling following ultrafast photoisomerization: Time-resolved infrared spectroscopy. The Journal of Physical Chemistry B. ISSN 1520-6106
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Abstract
The ultrafast photophysics of many isomerizing molecules involves subpicosecond formation of a twisted hot ground state, which transfers energy to the environment through vibrational relaxation (cooling) over several picoseconds. In time-resolved infrared (TR-IR) spectroscopy, hot ground state transients show frequency shifts and band reshapings, which cannot be described through kinetic models that assume static spectral functions. We report a simple anharmonic cascade framework, which uses a single adjustable parameter associated with scaling the probability of vibrational energy transfer to the environment, for describing hot ground state cooling (HGSC) in TR-IR spectroscopy. The model is demonstrated against measurements on the cyan fluorescent protein chromophore. To best describe HGSC band shape evolution, the model utilizes ab initio data on anharmonic vibrational structure and nonadiabatic molecular dynamics trajectories of S1→ S0 internal conversion for realistic vibration occupation numbers of the nascent hot ground state. The modeling framework is readily extended to include mode-specific rates for intermolecular energy transfer and can be applied to any ultrafast isomerizing molecule for which anharmonic vibrational properties can be computed.
| Item Type: | Article |
|---|---|
| Additional Information: | Funding information: This work was funded by an EPSRC New Investigator Award (EP/W018691 to J.N.B.), the Olle Engkvist Foundation (award 200-575 to M.H.S.), and an EPSRC grant (EP/X011410 to S.R.M.). V.J.E. acknowledges support from Chapman University, and acknowledges computer time from the Aiken cluster of the NASA Advanced Supercomputer (NAS). |
| Faculty \ School: | Faculty of Science > School of Chemistry, Pharmacy and Pharmacology Faculty of Science |
| UEA Research Groups: | Faculty of Science > Research Groups > Centre for Photonics and Quantum Science (former - to 2025) Faculty of Science > Research Groups > Chemistry of Light and Energy (former - to 2025) |
| Related URLs: | |
| Depositing User: | LivePure Connector |
| Date Deposited: | 16 Dec 2025 16:30 |
| Last Modified: | 16 Dec 2025 16:30 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/101436 |
| DOI: | 10.1021/acs.jpcb.5c07581 |
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